CN113354629B - Diaryl ethylene-naphthopyran dual photochromic compound and preparation method and application thereof - Google Patents
Diaryl ethylene-naphthopyran dual photochromic compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of organic light functional materials, in particular to a diarylethene-naphthopyran dual photochromic compound and a preparation method and application thereof.
Description
Technical Field
The invention relates to the field of organic optical functional materials, in particular to a diarylethene-naphthopyran double photochromic compound and a preparation method and application thereof.
Background
The organic photochromic material is used as an important optical functional material, has wide application prospect in the fields of photochromic glasses, intelligent windows, photochromic clothes, molecular switches, information storage, anti-counterfeiting materials and the like, and continuously draws attention of scholars in the fields of chemistry, materials, information and the like. The color change mechanism of the organic photochromic material is mainly divided into a P-type and a T-type. The P-type photochromic material is characterized in that the photochromic phenomenon is generated under the illumination of a certain wavelength, the photochromic body of the P-type photochromic material is faded under the illumination of another wavelength, and the photochromic body of the P-type photochromic material is stable to heat. The P-type photochromic compounds include diarylethene compounds, azobenzenes, fulgides, and the like. The T-type photochromic material is a material which generates a color change phenomenon when irradiated at a certain wavelength and fades when heated or irradiated at another wavelength, and the color change body of the material is unstable to heat. The T-type photochromic compound includes naphthopyrans, spirooxazines and the like. Currently, the photochromic materials reported in the literature generally only contain one photochromic structural unit, i.e. have the properties of a single P-type or T-type material, which limits the range of applications.
The diarylethene photochromic compound is a P-type photochromic material, which generates a color-changing body through a circumferential reaction under the irradiation of ultraviolet light and a reversible ring-opening reaction under the irradiation of visible light. The material has the advantages of excellent fatigue resistance, quick optical response, thermal stability and the like, and has application prospects in the fields of information storage, molecular switches and the like. The indene thick naphthopyran photochromic compound belongs to a T-type photochromic material, and is subjected to heterolytic ring-opening reaction under the irradiation of visible light, a colorless body is converted into a colored body, and a ring-closing reaction is carried out under heating (room temperature) to generate the colorless body. The material has the advantages of high chromaticity, quick photoresponse, good fatigue resistance and the like, and is applied to the fields of color-changing glasses and the like.
The development of photochromic materials with fast response, fast fading and multiple functions is one of the research hotspots of organic functional materials in recent years. Chinese patent CN105175431B filed in 2015 provides a bifunctional photochromic compound, a synthesis method and an application thereof, the photochromic material contains spirooxazine and diarylethene, a typical preparation method of the bifunctional photochromic compound is that 2-nitroso-1, 2-diarylethenol and indoline derivatives are subjected to condensation reaction to obtain a target compound, and the synthesized bifunctional photochromic compound has potential application in photochromic materials and information storage. However, the invention does not realize the regulation of the color change property of the material through the light irradiation or heating conditions with different wavelengths, has single performance and limits the practical application range.
The diarylethene and the indene thick naphthopyran are two types of common photochromic materials, wherein the diarylethene photochromic material changes color under ultraviolet illumination, fades under visible light illumination and has thermal stability; the naphthopyran photochromic material changes color under the irradiation of visible light, fades by heating and is unstable to heat. At present, no technology for preparing bifunctional photochromic compounds by using diarylethene and indene fused naphthopyran is available. The invention designs and synthesizes a novel dual photochromic compound by combining the characteristics of diarylethene type and indene thick naphthopyran type compounds, can regulate and control the color-changing property by light irradiation with different wavelengths and heating conditions, and can be used in the fields of multiple anti-counterfeiting materials, color-changing glasses, color-changing clothes and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a diarylethene-naphthopyran double-photochromic compound (shown in formula I) and a preparation method and application thereof, the photochromic performance of the compound can be controlled by ultraviolet light and visible light, the compound has the advantages of quick photoresponse, quick fading and the like, and has application prospects in the fields of multiple anti-counterfeiting materials, photochromic glasses, photochromic clothes and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a diarylethene-naphthopyran dual-photochromic compound has a structure shown in formula I:
wherein R = CH 3 O,CH 3 ,H,F,Cl,CF 3 ,NO 2 。
The invention also provides a preparation method of the dual photochromic compound I, and the synthetic process route is as follows:
(1) Preparing an intermediate compound C from the compound A and a 4-bromobenzophenone derivative B under the action of a palladium catalyst and an inorganic base, wherein the reaction formula is as follows:
(2) Preparing a compound D from the compound C and trimethylsilylacetylene under the action of organic base, wherein the reaction formula is as follows:
(3) Preparing a diarylethene-naphthopyran dual photochromic compound I from the compound D and the compound E under the catalysis of acid, wherein the reaction formula is as follows:
in the step (1), the molar ratio of the A to the B is 1 to 2, the dosage of the palladium catalyst is 1-5% of the total molar amount of the reactants, the molar ratio of the dosage of the inorganic base to the total molar amount of the reactants is 5-6, the reflux temperature is 80 ℃, the reaction time is 30-40h, the reaction is carried out under the protection of nitrogen, the reaction process is monitored by TLC, and the solid obtained by separation and purification is a compound C.
Wherein the palladium catalyst is any one of palladium acetate, tetrakis (triphenylphosphine) palladium and palladium dichloride; the alkali is any one of potassium carbonate, sodium carbonate and cesium carbonate; the solvent is a mixed solvent of tetrahydrofuran and water according to a volume ratio of 3.
Preferably, the purification process of compound C is: cooling the system to room temperature after the reaction is finished, extracting by ethyl acetate, washing by water, combining organic phases, and anhydrous MgSO 4 Drying, suction filtering, removing solvent with rotary evaporator, and separating the crude product with silica gel column chromatography to obtain C.
In the step (2), under the protection of nitrogen, dropwise adding an organic base solution into a trimethylsilylacetylene solution dissolved in a solvent at-70 to-78 ℃, preferably at-78 ℃, reacting for 1 hour, dropwise adding a compound C solution dissolved in the solvent into a system for reaction at room temperature, monitoring the reaction process by TLC until the reaction is finished, and separating and purifying to obtain an oily liquid, namely a compound D;
wherein the molar ratio of the trimethylsilylacetylene to the compound C to the organic base is 4.
Preferably, the purification process of compound D is: after the reaction is finished, adding a methanol solution of potassium hydroxide, and stirring for 30 minutes; pouring the system into saturated ammonium chloride solution, extracting with ethyl acetate for three times, combining organic phases, washing the organic phases with water and saturated saline water respectively, and washing the organic phases with anhydrous MgSO 4 Drying, suction filtering, rotary evaporating to remove solvent, and separating the crude product by silica gel column chromatography to obtain oily liquid D.
In the step (3), D and E are dissolved in a solvent according to a molar ratio of 1.
Preferably, the purification process of compound I is: cooling the reacted system to room temperature, adding water, extracting with ethyl acetate three times, combining organic phases, anhydrous MgSO 4 Drying, filtering, removing the solvent by rotary evaporation, and separating the crude product by silica gel column chromatography to obtain powder I.
The eluent used for the silica gel column chromatography separation in the steps (1) (2) (3) is petroleum ether/ethyl acetate =10-1 (V/V).
The invention also provides application of the diarylethene-naphthopyran double photochromic compound shown in the formula I in the aspect of multiple anti-counterfeiting materials.
The invention also provides an application of the diarylethene-naphthopyran double photochromic compound shown in the formula I in the aspect of information storage materials.
The invention has the beneficial effects that: the diaryl ethylene-naphthopyran double photochromic compound is prepared by the synthesis method, the compound is light purple or green, the tetrahydrofuran solution of the compound is colorless before illumination, and the compound has a diaryl ethylene structure and a naphthopyran structure simultaneously, so that the compound can respond to ultraviolet light, visible light and heat (the visible light irradiating solution changes from colorless to purple, the solution changes from colorless to red when the ultraviolet light irradiates, the color fades after being placed in a dark place or heated), and the response is rapid, so that the photochromic performance of the compound can be controlled by the ultraviolet light and the visible light, the compound has the characteristics of light bottom color, high chroma after discoloration and the like, and has wide application prospect in the fields of sun protection glasses, intelligent glass, color-changing clothing, multiple anti-counterfeiting materials and the like.
Drawings
FIG. 1 shows Ib (1X 10) -5 M) irradiating the tetrahydrofuran solution with visible light (400 nm) for different time of ultraviolet visible absorption spectrum;
FIG. 2 isIb(1×10 -5 M) irradiating the tetrahydrofuran solution with ultraviolet light (254 nm) for different time of ultraviolet visible absorption spectrum;
FIG. 3 shows Ib (1X 10) after irradiation with visible light (400 nm) -5 M) UV-visible absorption spectrum of the fading process of the tetrahydrofuran solution;
FIG. 4 shows Ib (1X 10) after exposure to UV light (254 nm) -5 M) uv-vis absorption spectrum of the fading process of the tetrahydrofuran solution.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail with reference to the accompanying drawings, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is to be noted that the compound a involved in the first reaction step of the present invention was prepared with reference to the prior art (yes pigm.,2018, 159. The drugs and reagents used in the reaction are well known in the art and are commercially available.
Example 1 Synthesis of diarylethene-naphthopyran Dual photochromic Compounds Ia
The first step is as follows: synthesis of intermediate Compound C1
To a 50mL three-necked flask, a 0.10g (0.29 mmol), (4-bromophenyl) (phenyl) methanone b10.15g (0.58 mmol), potassium carbonate 0.68g (4.9 mmol), and tetrakis (triphenylphosphine) palladium 0.02g (0.02 mmol), 10mL of a tetrahydrofuran/water mixed solvent (volume ratio = 3) were added under nitrogen protection, and the reaction progress was monitored by TLC at 80 ℃. After the reaction, the system was cooled to room temperature, extracted with ethyl acetate (30 mL. Times.3), washed with water, and the organic phases were combined and anhydrous MgSO 4 Drying, suction filtering, and removing the solvent by a rotary evaporator. Crude product ofThe column was chromatographed on silica gel with a eluent of petroleum ether/ethyl acetate (vol =6 = 1) to give a dark blue solid, c10.12g, in 64% yield.
The dark blue solid obtained is treated with CDCl 3 As a solvent, respectively 1 H NMR measurement of 13 C NMR test, and the obtained nuclear magnetic data are characterized as follows, and the structural formula is shown as C1.
The nuclear magnetic resonance hydrogen spectrum data of C1 is characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ7.81-7.78(m,8H),7.60-7.57(m,6H),7.50(s,1H),7.48(s,2H),7.46(s,1H),7.17(s,2H),2.87(t,J＝8Hz,4H),2.11(m,J＝8Hz,2H),2.04(s,6H).
the nuclear magnetic resonance carbon spectrum data of C1 is characterized in that: 13 C NMR(101MHz,CDCl 3 )δ195.93,138.45,138.36,137.80,137.10,136.48,135.62,134.80,132.31,130.98,129.92,128.30,125.57,124.76,38.48,23.04,14.67.
the second step is that: synthesis of Compound D1
Under the protection of nitrogen, 0.88mL (6.3 mmol) of trimethylsilylacetylene and 50mL of tetrahydrofuran were added to a 250mL three-necked flask, the system was moved to-78 ℃,2.5 mL (6.3 mmol, 2.5M) of a tetrahydrofuran solution of t-butyllithium was added dropwise, and the reaction was continued for 1 hour after the addition. C10.97g (1.56 mmol) was dissolved in 20mL tetrahydrofuran and added slowly dropwise to the reaction flask. The reaction was carried out at room temperature for 4 hours and the progress of the reaction was monitored by TLC. After the reaction was completed, 10mL of a methanolic solution of potassium hydroxide was added and stirring was continued for 30 minutes. The system was poured into 50mL of a saturated ammonium chloride solution, and extracted with ethyl acetate (30 mL. Times.3). The organic phases were combined, washed with 30mL of water, 30mL of saturated brine, and anhydrous MgSO 4 And (5) drying. Suction filtration and rotary evaporator to remove solvent. The crude product was isolated by silica gel column chromatography with a eluent of a petroleum ether/ethyl acetate mixed solvent (volume =6: 1) to give 0.78g of a pale red oily liquid with a yield of 74%.
The resulting pale red oily liquid was treated with CDCl 3 As a solvent, are separately carried out 1 H NMR test and 13 c NMR test, and the obtained nuclear magnetic data are characterized as follows, and the structural formula is shown as D1.
The nuclear magnetic resonance hydrogen spectrum data of D1 are characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ7.63-7.61(m,4H),7.56-7.54(m,4H),7.45-7.43(m,4H),7.36-7.32(m,4H),7.30-7.28(m,2H),7.00(s,2H),2.89(s,2H),2.82(t,J＝8Hz,4H),2.07(m,J＝8Hz,2H),1.96(s,6H).
the nuclear magnetic resonance carbon spectrum data of D1 are characterized as follows: 13 C NMR(101MHz,CDCl 3 )δ144.22,143.03,139.02,137.43,136.70,134.76,134.63,134.08,128.39,127.96,126.44,125.92,125.19,124.23,86.06,75.64,74.10,38.44,14.51.
the third step: synthesis of diarylethene-naphthopyran dual photochromic compounds Ia
In a 100mL single-neck bottle, D10.15g (0.22 mmol) was dissolved in 40mL of toluene, 0.13g (0.49 mmol) of E was added, and after stirring uniformly, 1 to 2 drops of an acid catalyst, dodecylbenzenesulfonic acid, were added dropwise. The reaction mixture was heated to 40 ℃ for 3 hours, cooled to room temperature, and 20mL of water was added to the reaction mixture. Extracted with ethyl acetate (30 mL. Times.3), and the organic phases were combined, anhydrous MgSO 4 And (5) drying. Filtered and the solvent removed by rotary evaporator. The crude product was separated by column chromatography on silica gel with a eluent of a mixed solvent of petroleum ether/ethyl acetate (volume ratio =6 = 1), yielding 71mg of a pale purple powder with a yield of 28%.
The resulting pale purple powder was treated with CDCl 3 As a solvent, are separately carried out 1 H NMR measurement and 13 c NMR measurement, and the obtained nuclear magnetic data are characterized as follows, and the structural formula is shown as Ia.
The nuclear magnetic resonance hydrogen spectrum data of Ia are characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ8.65(d,J＝8Hz,4H),8.48(d,J＝8Hz,2H),8.44(d,J＝8Hz,2H),8.20(d,J＝8Hz,4H),7.60-7.36(m,22H),6.96(s,2H),6.26(d,J＝8Hz,2H),6.22(d,J＝8Hz,2H),2.78(t,J＝8Hz,4H),2.03(m,2H),1.90(s,6H),1.65(s,6H),1.64(s,6H).
nuclear magnetic resonance of IaThe vibro-carbonaceous spectra data are characterized as: 13 C NMR(101MHz,CDCl 3 )δ154.90,148.24,148.13,147.44,144.79,144.53,143.95,143.48,139.85,139.79,139.07,136.62,134.62,134.60,134.48,133.71,130.56,130.09,128.22,128.20,127.71,127.67,127.62,127.54,127.45,127.35,127.16,127.12,127.03,126.99,126.79,126.76,125.45,125.41,125.02,124.88,124.85,124.77,124.71,124.05,123.71,123.13,123.08,122.04,121.83,121.14,121.08,113.06,112.96,82.28,82.16,47.65,38.45,26.90,26.13,14.40.
example 2 Synthesis of diarylethene-naphthopyran Dual photochromic Compounds Ib
The first step is as follows: synthesis of intermediate compound C2
To a 100mL three-necked flask, a 0.5g (1.4 mmol), (4-bromophenyl) (4-methoxyphenyl) methanone b20.83g (2.8 mmol), potassium carbonate 3.38g (24.4 mmol), and tetrakis (triphenylphosphine) palladium 0.12g (0.1 mmol), 45mL of a tetrahydrofuran/water mixed solvent (volume ratio = 3) were added under nitrogen protection, refluxed at 80 ℃ for 36 hours, and the progress of the reaction was monitored by TLC. Cooling the system to room temperature after the reaction is finished, extracting by ethyl acetate, washing by water, combining organic phases, and carrying out anhydrous MgSO 4 Drying, suction filtering, and removing the solvent by a rotary evaporator. The crude product was isolated by silica gel column chromatography eluting with petroleum ether/ethyl acetate (vol =6: 1) to give a light blue solid 0.44g with a yield of 45%.
The resulting pale blue solid was treated with CDCl 3 As a solvent, are separately carried out 1 H NMR measurement and 13 c NMR test, and the obtained nuclear magnetic data are characterized as follows, and the structural formula is shown as C2.
Nuclear magnetic resonance hydrogen spectrum data of C2 are characterized as: 1 H NMR(400MHz,CDCl 3 )δ7.82(d,J＝8Hz,4H),7.75(d,J＝8Hz,4H),7.58(d,J＝8Hz,4H),7.17(s,2H),6.96(d,J＝8Hz,4H),3.88(s,6H),2.86(t,J＝8Hz,4H),2.12(m,J＝8Hz,2H),2.04(s,6H).
the nuclear magnetic resonance carbon spectrum data of C2 is characterized as follows: 13 C NMR(101MHz,CDCl 3 )δ194.70,163.15,138.55,137.89,137.07,136.34,136.25,134.80,132.41,130.66,130.31,125.42,124.71,113.58,55.50,38.48,23.05,14.61.
the second step is that: synthesis of Compound D2
Under the protection of nitrogen, 0.36mL (2.6 mmol) of trimethylsilylacetylene and 60mL of tetrahydrofuran were added to a 250mL three-necked flask, the system was moved to-78 ℃, 1.03mL (2.6 mmol, 2.5M) of butyllithium in tetrahydrofuran was added dropwise, and the reaction was carried out for 1 hour after completion of the dropwise addition. C20.44g (0.65 mmol) was dissolved in 20mL tetrahydrofuran and added slowly dropwise to the flask. The reaction was carried out at room temperature for 5 hours and the progress of the reaction was monitored by TLC. After the reaction was completed, 10mL of a methanolic solution of potassium hydroxide was added, and stirring was continued for 30 minutes. The system was poured into 50mL of saturated ammonium chloride solution and extracted with ethyl acetate (30 mL. Times.3). The organic phases were combined, washed with 30mL of water, 30mL of saturated brine, and anhydrous MgSO 4 And (5) drying. Suction filtration and rotary evaporator to remove solvent. The crude product was isolated by silica gel column chromatography with eluent of petroleum ether/ethyl acetate mixed solvent (volume ratio =6 = 1), yielding 0.38g of light red oily liquid with a yield of 80%.
The resulting pale red oily liquid was treated with CDCl 3 As a solvent, respectively 1 H NMR measurement of 13 C NMR test, and the obtained nuclear magnetic data are characterized as follows, and the structural formula is shown as D2.
The nuclear magnetic resonance hydrogen spectrum data of D2 are characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ7.53-7.48(m,8H),7.44-7.41(m,4H),7.00(s,2H),6.82(d,J＝8Hz,4H),3.74(s,6H),3.10(s,2H),2.81(t,J＝8Hz,4H),2.05(m,J＝8Hz,2H),1.96(s,6H).
the nuclear magnetic resonance carbon spectrum data of D2 is characterized as follows: 13 C NMR(101MHz,CDCl 3 )δ171.37,159.20,143.43,139.16,136.74,134.67,133.95,130.79,127.40,126.47,125.16,124.21,113.66,86.53,75.41,73.74,60.52,55.31,38.48,21.09.
the third step: synthesis of diarylethene-naphthopyran dual photochromic compound Ib
In a 100mL single-neck flask, D20.08g (0.11 mmol) is dissolved in 40mL of toluene, 0.06g (0.24 mmol) of E is added, and after stirring uniformly, 1-2 drops of an acid catalyst, namely dodecylbenzene sulfonic acid, are added dropwise. The reaction mixture was heated to 40 ℃ for 3 hours, cooled to room temperature, and 20mL of water was added to the reaction mixture. Extracted with ethyl acetate (30 mL. Times.3), and the organic phases were combined, anhydrous MgSO 4 And (5) drying. Filtered and the solvent removed by rotary evaporator. The crude product was separated by column chromatography on silica gel with a eluent of a mixed solvent of petroleum ether/ethyl acetate (volume ratio =6 = 1), yielding 53mg of pale purple powder with a yield of 40%.
The resulting pale purple powder was treated with CDCl 3 As a solvent, respectively 1 H NMR measurement and 13 c NMR test, the obtained nuclear magnetic data are characterized as follows, and the structural formula is shown as Ib.
The nuclear magnetic resonance hydrogen spectrum data of Ib are characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ8.53(d,J＝8Hz,2H),8.35(d,J＝8Hz,2H),8.08(d,J＝8Hz,2H),7.48-7.44(m,2H),7.39-7.24(m,17H),7.19-7.12(m,5H),6.86(s,2H),6.72-6.69(m,4H),6.10(d,J＝8Hz,2H),3.62(s,6H),2.67(t,J＝8Hz,4H),1.90(m,2H),1.80(s,6H),1.53(s,12H).
the nuclear magnetic resonance carbon spectrum data of Ib are characterized as follows: 13 C NMR(101MHz,CDCl 3 )δ157.94,153.88,147.26,146.44,142.79,138.85,138.12,135.79,135.61,133.55,133.48,132.58,129.55,129.06,127.24,126.85,126.60,126.22,126.07,125.96,125.89,124.37,123.99,123.79,123.01,122.68,122.13,121.00,120.79,119.86,112.49,112.05,81.11,54.15,46.63,37.44,28.67,25.09,21.89,13.39.
example 3 Synthesis of diarylethene-naphthopyran Dual photochromic Compounds Ic
The first step is as follows: synthesis of intermediate compound C3
To a 100mL three-necked flask, a 0.57g (1.6 mmol), (4-bromophenyl) (4-nitrophenyl) methanone b31.00g (3.3 mmol), potassium carbonate 3.87g (27.9 mmol), and tetrakis (triphenylphosphine) palladium 0.19g (0.16 mmol), 45mL of a tetrahydrofuran/water mixed solvent (volume ratio = 3), was added under nitrogen protection, and refluxed at 80 ℃ for 36 hours, and the progress of the reaction was monitored by TLC. Cooling the system to room temperature after the reaction is finished, extracting by ethyl acetate, washing by water, combining organic phases, and anhydrous MgSO 4 Drying, suction filtering and removing the solvent by a rotary evaporator. The crude product was isolated by silica gel column chromatography eluting with petroleum ether/ethyl acetate (vol = 8.
The resulting pale green solid was treated with CDCl 3 As a solvent, respectively 1 HNMR test and 13 c NMR test, the obtained nuclear magnetic data are characterized as follows, and the structural formula is shown as C3.
The nuclear magnetic resonance hydrogen spectrum data of C3 is characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ8.35(d,J＝8Hz,4H),7.92(d,J＝8Hz,4H),7.78(d,J＝8Hz,4H),7.61(d,J＝8Hz,4H),7.20(s,2H),2.86(t,4H),2.12(m,2H),2.05(s,6H).
the nuclear magnetic resonance carbon spectrum data of C3 is characterized as follows: 13 C NMR(101MHz,CDCl 3 )δ193.88,149.76,143.16,139.33,138.05,137.25,137.10,134.86,134.25,131.02,130.55,126.03,125.00,123.59,38.48,23.03,14.68.
the second step is that: synthesis of Compound D3
Under the protection of nitrogen, 0.28mL (2.0 mmol) of trimethylsilylacetylene and 40mL of tetrahydrofuran were added to a 100mL three-necked flask, the system was moved to-78 ℃, 0.80mL (2.0 mmol, 2.5M) of a butyllithium n-hexane solution was dropwise added, and the reaction was carried out for 1 hour after completion of the dropwise addition. C30.36g (0.50 mmol) is dissolved in 20mL tetrahydrofuran and slowly added dropwise to the reaction flask. The reaction was carried out at room temperature for 5 hours and the progress of the reaction was monitored by TLC. After the reaction was completed, 10mL of a methanolic solution of potassium hydroxide was added, and stirring was continued for 30 minutes.The system was poured into 50mL of a saturated ammonium chloride solution, and extracted with ethyl acetate (30 mL. Times.3). The organic phases were combined, washed with 30mL of water, 30mL of saturated brine, and anhydrous MgSO 4 And (5) drying. Suction filtration and rotary evaporator to remove solvent. The crude product was isolated by silica gel column chromatography with a eluent of a mixed solvent of petroleum ether/ethyl acetate (volume ratio =2: 1) to give 0.14g of a pale purple oily liquid with a yield of 36%.
The resulting pale purple oily liquid was treated with CDCl 3 As a solvent, are separately carried out 1 H NMR measurement and 13 c NMR test, and the obtained nuclear magnetic data are characterized as follows, and the structural formula is shown as D3.
The nuclear magnetic resonance hydrogen spectrum data of the D3 are characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ8.16(d,J＝8Hz,4H),7.78(d,J＝8Hz,4H),7.53(d,J＝8Hz,4H),7.44(d,J＝8Hz,4H),7.00(s,2H),3.34(s,2H),3.24(s,2H),2.82(t,J＝8Hz,4H),2.08(m,2H),1.98(s,6H).
the nuclear magnetic resonance carbon spectrum data of D3 are characterized as follows: 13 C NMR(101MHz,CDCl 3 )δ171.30,151.10,147.38,141.78,138.60,136.79,135.15,134.71,131.07,126.88,126.38,125.43,124.55,123.64,84.92,73.61,60.47,38.40,23.01,21.08.
the third step: synthesis of diarylethene-naphthopyran dual photochromic compound Ic
D30.14g (0.21 mmol) was dissolved in 40mL of toluene in a 100mL single-neck flask, 0.10g (0.42 mmol) of E was added thereto, and after stirring the mixture uniformly, 1 to 2 drops of dodecylbenzenesulfonic acid as an acid catalyst were added dropwise. The reaction mixture was heated to 40 ℃ for 3 hours, cooled to room temperature, and 20mL of water was added to the reaction mixture. Extracted with ethyl acetate (30 mL. Times.3), and the organic phases were combined, anhydrous MgSO 4 And (5) drying. Filtered and the solvent removed by rotary evaporator. The crude product was separated by column chromatography on silica gel with a eluent of a mixed solvent of petroleum ether/ethyl acetate (volume ratio =4 = 1), yielding 109mg of pale green powder in 48% yield.
The resulting pale green powder was washed with CDCl 3 To dissolveAgents, respectively carrying out 1 H NMR measurement and 13 c NMR test, the obtained nuclear magnetic data is characterized as follows, and the structural formula is shown as Ic.
The nuclear magnetic resonance hydrogen spectrum data of Ic is characterized as: 1 HNMR(400MHz,CDCl 3 )δ8.68(d,J＝8Hz,2H),8.45(d,J＝8Hz,2H),8.22-8.16(m,8H),7.75(s,2H),7.72(s,2H),7.62(t,J＝8Hz,4H),7.53(t,J＝8Hz,4H),7.48-7.38(m,6H),7.31(t,J＝8Hz,4H),6.98(s,2H),6.23(d,J＝8Hz,2H),2.78(t,J＝8Hz,4H),2.03(m,2H),1.91(s,6H),1.65(s,6H),1.64(s,6H).
the nuclear magnetic resonance carbon spectrum data for Ic is characterized by: 13 C NMR(101MHz,CDCl 3 )δ154.81,151.86,147.65,147.31,147.20,141.98,139.56,138.67,136.69,134.96,134.52,134.32,131.76,130.21,127.67,127.63,127.46,127.21,127.08,126.80,126.29,125.71,125.27,125.22,124.58,124.32,124.16,123.91,123.66,123.53,122.78,122.34,122.18,121.88,113.07,81.70,47.67,38.43,26.14,14.42.
in order to illustrate the discoloration property and discoloration response speed of the photochromic compound obtained in the present invention, examples 4 to 7 were further tested by taking the photochromic compound Ib as an example.
Example 4 photochromic Properties of photochromic Compound Ib under visible light irradiation
Adopts spectral pure tetrahydrofuran as solvent to prepare tetrahydrofuran solution (1 × 10) of compound Ib -5 M). The photochromic properties of compound Ib under visible light (lambda =400 nm) irradiation were first examined using an Analytikjena specord 210 plus type UV-visible spectrophotometer with a hundred million-ohm Xe-150 xenon lamp as the light source (electric power 300w, optical power 50w, spectral range 200nm-2500 nm). FIG. 1 shows Ib (1X 10) -5 M) in a tetrahydrofuran solution, and the ultraviolet-visible absorption spectra of the solution were observed under visible light (400 nm) for different periods of time, as shown in FIG. 1, ib (1X 10) in the absence of light -5 M) is colorless, has no absorption peak in the range of 400-800nm, and when irradiated with visible light, the solution turns purple, while generating a strong absorption peak at 551nm, which is caused by the open ring structure of naphthopyran. When the solution is irradiated for 60 seconds, the absorbance of the solution reaches the maximum saturation value, and the light response is quick.
Example 5 photochromic Properties of photochromic Compound Ib under UV light (lambda =254 nm)
Preparing tetrahydrofuran solution (1 × 10) of compound Ib by using spectrally pure tetrahydrofuran as solvent -5 M). The photochromic properties of compound Ib under uv light (λ =254 nm) irradiation were examined, and the apparatus and light source conditions were the same as in example 4.Ib (1X 10) - 5 M) in a tetrahydrofuran solution, as shown in FIG. 2, in ultraviolet light (254 nm) at different times of irradiation, ib (1X 10) -5 M) generating an absorption peak at 551nm by the tetrahydrofuran solution of the M), wherein the absorption peak is caused by ring opening reaction of a naphthopyran structural unit; meanwhile, a new absorption peak is generated at 360nm, and the absorption peak is caused by a ring closure reaction of a dithienyl ethylene structural unit. The solution changes from colorless to red, and with reference to fig. 1, it is shown that different photochemical reactions can occur to display different colors by using different wavelengths of light. The maximum absorbance value is reached when the light source irradiates for 30 seconds, and the light response is quicker compared with visible light, so that the color change property can be regulated and controlled through the light with different wavelengths.
Example 6 thermochromic discoloration Properties of photochromic Compound Ib after discoloration under visible light irradiation
Preparing tetrahydrofuran solution (1 × 10) of compound Ib by using spectrally pure tetrahydrofuran as solvent -5 M). The thermal fading property of compound Ib after reaching the maximum absorbance under visible light (400 nm) irradiation was examined, and the apparatus and light source conditions were the same as those of example 4. The test method is that firstly Ib (1X 10) is irradiated by visible light (400 nm) -5 M) for 60 seconds, the maximum absorbance is reached, and then the uv-vis absorption spectrum is measured every 30 seconds in the dark. Obtaining Ib (1X 10) after visible light (400 nm) illumination -5 M) as shown in FIG. 3 (curves from top to bottom are UV-VIS absorption spectra for 0s,30s,60s,90s,120s, \ 8230; 600s, respectively, after saturation with light and dark). FIG. 3 shows the fade half-life t of the compound 1/2 108s, has a faster fading speed.
Example 7 thermochromic Properties of photochromic Compound Ib after discoloration by ultraviolet light irradiation
Adopts spectral pure tetrahydrofuran as solvent to prepare tetrahydrofuran solution (1 × 10) of compound Ib -5 M). The thermolytic bleaching property of the compound Ib after the maximum absorbance is reached by the irradiation of ultraviolet light (254 nm) is examined. The apparatus and light source conditions were the same as in example 4. The test method comprises irradiating Ib (1 × 10) with ultraviolet light (254 nm) -5 M) for 30 seconds to reach the maximum absorbance, and then testing the ultraviolet visible absorption spectrum every 30 seconds in a dark state to obtain Ib (1 multiplied by 10) after being irradiated by ultraviolet light (254 nm) -5 M) in the tetrahydrofuran solution, as shown in FIG. 4 (curves from top to bottom are respectively UV-VIS absorption spectra of 0s,30s,60s,90s,120s, \8230; 600s after saturation with light and dark). FIG. 4 shows the fade half-life t of the compound 1/2 The fading speed is 282s, which is slower than that of visible light irradiation, which shows that the thermochromatic fading rate of the color-changing body is different when different wavelengths of light are irradiated, and the fading property can be regulated and controlled by the light irradiation with different wavelengths.
The research on the properties shows that the performance of the photochromic compound can be regulated and controlled by the illumination and heating conditions with different wavelengths, has different discoloration and fading rates, meets the performance requirements of multiple anti-counterfeiting materials and information storage materials, and has potential application value.
The above description is made in detail for the preferred embodiments of the present invention, but the above description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. A diarylethene-naphthopyran dual photochromic compound is characterized in that: the structure of the compound is shown as formula I:
wherein R = CH 3 O,CH 3 ,H,F,Cl,CF 3 ,NO 2 。
2. A method for preparing the dual photochromic compound of claim 1 comprising the steps of:
(1) Preparing an intermediate compound C from the compound A and a 4-bromobenzophenone derivative B under the action of a palladium catalyst and an inorganic base, wherein the reaction formula is as follows:
(2) Preparing a compound D from the compound C and trimethylsilylacetylene under the action of organic base, wherein the reaction formula is as follows:
(3) Preparing a diarylethene-naphthopyran dual photochromic compound I from the compound D and the compound E under the catalysis of acid, wherein the reaction formula is as follows:
wherein R = CH 3 O,CH 3 ,H,F,Cl,CF 3 ,NO 2 。
3. The production method according to claim 2, characterized in that: in the step (1), the molar ratio of the A to the B is 1-2, the dosage of the palladium catalyst is 1-5% of the total molar amount of the reactants, the molar ratio of the dosage of the inorganic base to the total molar amount of the reactants is 5-6, the reflux temperature is 80 ℃, the reaction time is 30-40h, the reaction is carried out under the protection of nitrogen, the reaction process is monitored by TLC, and the compound C is obtained after separation and purification.
4. The production method according to claim 2 or 3, characterized in that: the palladium catalyst is any one of palladium acetate, tetrakis (triphenylphosphine) palladium and palladium dichloride; the inorganic base is any one of potassium carbonate, sodium carbonate and cesium carbonate.
5. The production method according to claim 2, characterized in that: the solvent in the step (1) is a mixed solvent of tetrahydrofuran and water according to a volume ratio of 3.
6. The method of claim 2, wherein: in the step (2), under the protection of nitrogen, dropwise adding an organic base solution into a trimethylsilylacetylene solution, after reacting for 1 hour, dropwise adding a compound C solution into the system for reacting at room temperature, monitoring the reaction process by TLC until the reaction is finished, and separating and purifying to obtain a compound D; wherein the molar ratio of the trimethylsilylacetylene to the compound C to the organic base is 4.
7. The method of claim 6, wherein: the organic alkali is butyl lithium or tert-butyl lithium, and the dropping temperature is-70 ℃ to-78 ℃.
8. The production method according to claim 2, characterized in that: in the step (3), dissolving D and E in a solvent according to a molar ratio of 1:2.2, dropwise adding 1-2 drops of an acid catalyst, reacting at 40 ℃ for 3 hours, and separating and purifying to obtain the compound I.
9. The use of the diarylethene-naphthopyran-based dual photochromic compound of claim 1 in multiple security materials.
10. Use of the diarylethene-naphthopyran-based dual photochromic compound of claim 1 in information storage materials.
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